CN103341358A - Catalyst for treating chlorine-containing organic waste water, and preparation method thereof - Google Patents
Catalyst for treating chlorine-containing organic waste water, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for treating chlorine-containing organic waste water, and a preparation method thereof, belonging to the field of environmental technology. The catalyst comprises metal palladium and a carbonaceous carrier, and graphene is selected as the carbonaceous carrier. The preparation method of the catalyst comprises the steps of: firstly, conducting two-step oxidization on natural graphite to obtain oxidized graphite under the alkaline condition, and then conducting redox reaction to obtain the metal palladium/graphene-loaded catalyst. The evenly dispersed and uniformly-sized catalyst with palladium particles loaded on the graphene is prepared by taking graphene as a carrier, the particle size of metal component Pd is 3-8nm, and the catalyst is strong in adhesive force, high in dispersity, and high in effective utilization rate. The catalyst prepared by applying the preparation method is used as an electrochemical cathode to process the chlorinated organic compounds, so that the organic compounds are mineralized so as to achieve the purposes of thoroughly removing the pollutants and increasing the removal rate, and the catalyst has good application prospects and economic benefits on the aspect of sewage treatment.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method of handling chloride organic wastewater, particularly a kind of Catalysts and its preparation method of being combined with noble metal belongs to electrochemistry and Environmental Technology field.
Background technology
Understanding and research for chloro organic cpd just drew attention in recent years, and passing long-term and a large amount of use for chlorinatedorganic has caused a kind of potential threat to human and environment.The mankind do not have enough knowledge to chlorinatedorganic and pay attention to before, and the pollution that has caused chlorinatedorganic to bring is very serious.With regard to chlorinatedorganic itself, the cycle of its degraded is long, and easily extended residual is difficult for removing from environment, and can produces secondary pollution.
Because the amount in the sewage composition of chlorinatedorganic is fewer, and difficult removal, be a difficult problem for the scholar who studies processing method.At present, roughly can be summarized as for chloro organic cpd removal method: physics method, bioanalysis and chemical method.There is the cost height in the physics method, the problem of performance difficulty, and also the physics method is actually the transfer of pollutant, causes secondary pollution easily as careless manipulation.Because chloro organic cpd mostly is the artificial-synthetic compound, and is toxic to microorganism, so biodegradable application limitation is very big.Aerobe method can only be handled the few chlorinatedorganic of chlorine atom, though anaerobic degradation can make high chlorinatedorganic reduction dechlorination, can not make its thorough mineralising, and catabolite can be bigger than former parent product poison sometimes.The chemical combustion method is generally for the treatment of solid organic waste substances and high concentrated organic wastewaters such as Polychlorinated biphenyls, but this method itself can produce complicated chlorine-containing organic compounds.In recent years, handling chlorinatedorganic with electrochemical method is more and more paid attention to.The principle of electrochemical oxidation technology is to make oxidation operation under the electrocatalysis of electrode surface or under the free radical effect that is being produced by electric field action.Electrochemical oxidation technology produces strong oxidizer by electrode reaction, and be converted into the hydroxy radical (HO) of strong oxidability under suitable condition, make organic matter carry out oxidative degradation, again can be by selective catalyzed conversion on catalyst surface, thus reach the preferable organic effect of removal.With respect to other method of wastewater treatment, the electrochemical process simple equipments, easy to control, reaction condition is less demanding, carries out at normal temperatures and pressures.
Having now in electrochemical field utilizes the cathode oxidation method of reducing to handle the relevant patent of organic wastewater.For example: Chinese patent CN1101723486A discloses a kind of saliferous, the processing method of chlorine-contained wastewater, method with electrochemical catalytic oxidation is handled waste water, make pending chlorine-contained wastewater enter electrochemical reactor, regulating pH is 1～7, add one or more as-reduced metal ions as catalyst, catalyst amounts and chlorine ion concentration mol ratio are 1: 0.1～100, be negative electrode with the metal electrode, feed 0.1～1000A electric current, stop 15～90min after, regulate pH to 6～9 again, enter the flocculating setting pond, the time of staying is 5～600min, and this method needs adjusting pH twice, bring certain difficulty and current strength higher for practical operation technology, energy consumption is bigger.
And for example Chinese patent CN1017119810B discloses organic palladium catalyst of a kind of processing water containing chlorine and preparation method thereof, need under 90～100 ℃ of conditions, carry out the preliminary treatment of 1～3h to the carbonaceous carrier with salpeter solution, then under 75～85 ℃ of conditions, Metal Palladium is downloaded on the sour pretreated carbonaceous carrier, few alkaline solution that adds in this process, adopt the catalyst of preparation as negative electrode, with electrochemical method chlorinatedorganic is degraded.The method is in making the catalyst process, and concentrated acid is in hot stage operation inconvenience for a long time, and last TOC degradation rate is lower, and majority is lower than 80%, only up to 85%.
Have following problem with electrochemical method degradating chloro organic matter now as can be seen: (1) preparation catalyst condition is difficult for grasping the practical operation difficulty; (2) electrochemical degradation process complexity, even need carry out repeatedly preliminary treatment to waste water; (3) contaminant degradation is not thorough, and the TOC clearance is lower.
Summary of the invention
At the problems referred to above, the invention provides a kind of Catalysts and its preparation method of degradating chloro organic pollution, this catalyst is carbonaceous carrier to load metal palladium with the Graphene, with the catalyst of the present invention preparation as negative electrode, both had strong reduction dechlorination effect, can promote the molecular oxygen reduction to generate peroxide again, utilize the simultaneous oxidation of the electrochemistry cathodic reduction dechlorination harmonizing yinyang utmost point to combine, make chlorinatedorganic dechlorination detoxification under the reduction of negative electrode, chlorinatedorganic is thoroughly removed, improved the TOC clearance.
For realizing purpose of the present invention, one aspect of the present invention provides a kind of catalyst of degradating chloro organic pollution, is made up of Metal Palladium and carbonaceous carrier, and the carbonaceous carrier is selected Graphene, and the weight portion proportioning is 0.1～10: 100, is preferably 0.5～4: 100.
The present invention provides a kind of Preparation of catalysts method of degradating chloro organic pollution on the other hand, comprises following step in sequence:
1) native graphite is carried out oxidation in two steps, make graphite oxide;
2) palladium bichloride mixes with the graphene oxide dispersion liquid, carries out redox reaction with sodium borohydride, can obtain going back the ortho states palladium and be carried on Graphene.
Wherein, the two-step oxidation described in the step 1) is handled and is carried out according to the following steps order:
A) preparation pre-oxidation graphite: earlier sodium thiosulfate, phosphorus pentoxide are mixed back adding native graphite under 70～100 ℃ of conditions with the concentrated sulfuric acid and carry out pre-oxidation, reaction 4～10h filters and the washing filter residue, dries filter residue then, makes the preliminary treatment graphite oxide;
B) preparation graphite oxide: pre-oxidation graphite, potassium permanganate mixed with the concentrated sulfuric acid afterwards under 0～98 ℃ of condition, react 1～5h, add hydrogen peroxide and hydrochloric acid then, centrifugal and the gained colloid substance dried make graphite oxide.
Particularly, steps A) mass percent concentration of the concentrated sulfuric acid is 70～98% described in, is preferably 98%.
Wherein, the ratio of native graphite and the solid-liquid of the concentrated sulfuric acid is 1: 20～100 (namely when natural graphite quality was 1g, concentrated sulfuric acid volume was 20～100ml), was preferably 1: 30～50.
Wherein, the mass ratio of native graphite and sodium thiosulfate is 1: 2～10, is preferably 1: 6, and the mass ratio of native graphite and phosphorus pentoxide is 1: 2～10, is preferably 1: 6.
Wherein bake out temperature is 50～80 ℃, is preferably 60 ℃.
Particularly, step B) mass percent concentration of the concentrated sulfuric acid is 70～98% described in, is preferably 98%.
Wherein, the ratio of pre-oxidation graphite and the solid-liquid of the concentrated sulfuric acid is 1: 15～90 (namely when natural graphite quality was 1g, concentrated sulfuric acid volume was 15～90ml), was preferably 1: 20～50.
Wherein, pre-oxidation graphite is 1: 2～10 with the mass ratio of firm potassium manganate, is preferably 1: 6.
Particularly, earlier concentrated sulfuric acid temperature is down to 0～20 ℃, adds pre-oxidation graphite and potassium permanganate successively, keep temperature 0.5～2h.Temperature is risen to 30～50 ℃ then, keep 15～90min, persistently overheating to 90～98 ℃ afterwards.
Wherein the hydrogen peroxide mass percent concentration is 1～10%, and the hydrochloric acid mass percent concentration is 1～10%, is preferably 2～4%.
Particularly bake out temperature is 50～80 ℃, is preferably 60 ℃.
Wherein, the redox reaction described in the step 1) is carried out according to the following steps order:
A) graphite oxide and distilled water are carried out ultrasonic 0.5～4h, obtain the graphene oxide dispersion liquid;
B) with solid palladium chloride and alkene mixed in hydrochloric acid, be configured to solution, add the graphene oxide dispersion liquid then, mix;
C) add alkaline solution, the pH value of regulator solution is 9～10;
D) add sodium borohydride solution, carry out redox reaction;
E) reaction finishes that filter the back, the washing filter residue, and filter residue and drying is to constant weight, namely gets to go back the ortho states palladium and be carried on catalyst on the Graphene.
Particularly, steps A) solid-to-liquid ratio of graphite oxide and distilled water described in is 1: 100～2000, and (namely when the graphite oxide quality was 1g, the distilled water volume was 100～2000ml), was preferably 1: 500～1000.
Particularly, step B) the hydrochloric acid mass percent concentration is 0.1～1% in, is preferably 0.5%.
Wherein the ratio of solid palladium chloride and the solid-liquid of hydrochloric acid is 1: 100～2000 (namely when the palladium bichloride quality was 1g, the hydrochloric acid volume was 100～2000ml), was preferably 1: 500～1000.
Wherein the weight portion proportioning of palladium is 100 in graphite oxide and the palladium chloride solution: 0.1-10.
Particularly, step C) mass percent concentration of alkaline solution is 1～30% described in, and alkaline solution is selected NaOH or potassium hydroxide solution.
Particularly, step D) sodium borohydride solution described in is wanted earlier the distilled water temperature is reduced to 0～10 ℃, adds sodium borohydride solids then and stirs.
Wherein solid palladium chloride and sodium borohydride weight portion proportioning are 1: 10～200, be preferably 1: 50～and 100.
Particularly, step e) bake out temperature is 50～80 ℃ described in, is preferably 60 ℃.
Wherein, filter residue is washed with distilled water to that to flow out liquid pH be 7.
The present invention compared with prior art has following advantage:
1, Preparation of catalysts method technology of the present invention is simple, workable, is easy to enlarge produce.By using the reducing property of solvent, under the condition of gentleness, at reducing metal palladium particle simultaneously, graphene oxide is reduced to Graphene.The Metal Palladium particle size that loads on the Graphene surface is even, is about 6nm through characterizing metal palladium average particle size, can give full play to the catalytic action of palladium.
2, the open catalyst activity height of the present invention as electrochemistry negative electrode degraded chlorinatedorganic clearance height, reaches 96%～100%; Dechlorination rate reaches 88%～100%; The TOC clearance reaches 91%～98%.
3, the catalyst of using the present invention's preparation is handled chloro-organic waste water as the electrochemistry negative electrode, feed hydrogen earlier and carry out hydrogenation-dechlorination, back bubbling air carries out oxidation reaction, make mineralization of organic material, reach the purpose of thorough removal pollutant and raising clearance, aspect sewage disposal, have application promise in clinical practice and economic benefit.
Description of drawings
Figure is transmission electron microscope (TEM) figure of embodiment 1 obtained graphene-supported palladium catalyst.
The specific embodiment
For better understanding content of the present invention, below in conjunction with embodiment technical scheme of the present invention is described further, but the cited case does not limit protection scope of the present invention.
Embodiment 1
1, preparation graphite oxide
1) potassium thiosulfate and phosphorus pentoxide are joined in the concentrated sulfuric acid that is stirring, be warmed up to 80 ℃ after waiting to stir, remain on 80 ℃ of stir process 1h.Native graphite joins in 80 ℃ the mixed solution, remain on 80 ℃ and stir 6h, be cooled to room temperature, wherein, concentrated sulfuric acid concentration is 98%, the solid-to-liquid ratio of native graphite and the concentrated sulfuric acid is 1: 30, and native graphite and potassium thiosulfate weight ratio are 1: 6, and native graphite and phosphorus pentoxide weight ratio are 1: 6.
2) filter behind the cool to room temperature, place 60 ℃ to dry to constant weight the filter residue after the washing, obtain pre-oxidation graphite.
3) pre-oxidation graphite is joined in the concentrated sulfuric acid of ice-water bath, add potassium permanganate then, remain on 20 ℃ and stir 2.5h, temperature is risen to 35 ℃ then, keep 30min, persistently overheating to 95 ℃ afterwards, keep 30min, add hydrogen peroxide, add hydrochloric acid then, wherein concentrated sulfuric acid concentration is 98%, and the solid-to-liquid ratio of pre-oxidation graphite and the concentrated sulfuric acid is 1: 25, and pre-oxidation graphite and potassium permanganate weight ratio are 1: 6, hydrogen peroxide concentration is 3%, pre-oxidation graphite and hydrogen peroxide solid-to-liquid ratio are 1: 50, and concentration of hydrochloric acid is 3%, and hydrogen peroxide and hydrochloric acid volume ratio are 1: 10.
4) product is centrifugal, the gained colloid substance is dried to constant weight at 60 ℃, obtain graphite oxide.
2, make the graphene oxide dispersion liquid
Get 0.3g graphite oxide and 300ml distilled water, the graphene oxide dispersion liquid of ultrasonic 1h, wherein graphite oxide and distilled water solid-to-liquid ratio are 1: 1000.
3, configuration palladium chloride solution
Get the 0.010g solid palladium chloride and add 10ml watery hydrochloric acid, be stirred to clear solution, wherein the solid-to-liquid ratio of solid palladium chloride and watery hydrochloric acid is that 1: 1000 alkene concentration of hydrochloric acid is 0.5%, the content of palladium is 59% in the solid palladium chloride, and the ratio that contains the weight of palladium in the weight of graphite oxide and the palladium chloride solution is 100: 2.0.
4, prepare graphene-supported palladium catalyst
1) add the 0.5mol/L sodium hydroxide solution, pH transfers to 10 with the graphene oxide dispersion liquid.
2) palladium chloride solution is joined the graphene oxide dispersion liquid, stir 1h.
3) get 20ml distilled water, be placed in the mixture of ice and water and lower the temperature, slowly add the 1g sodium borohydride and be stirred to dissolving fully simultaneously.
4) sodium borohydride solution is joined in the graphite oxide dispersion liquid, stir 5h.
5) reaction finishes the back filtration, a large amount of distilled water washing filter residues, and the outflow liquid pH after washing is 7.
6) filter residue is dried to constant weight under 60 ℃, makes the Graphene carried palladium catalyst.
Adopt present embodiment to prepare catalyst and make the electro-catalysis negative electrode, handle 4-chlorophenol solution with electrochemical method, formerly feed hydrogen, under the condition of back aerating oxygen, handle through 100min, 4-chlorophenol clearance reaches 97.5%, the chlorine clearance reaches 96.8%, TOC clearance and reaches 94.4%.
Adopt the Graphene carried palladium catalyst surface topography of transmission electron microscope (TEM) sweep measuring preparation, the analysing particulates size, its electron scanning Electronic Speculum figure is as shown in the figure.
Embodiment 2
1, preparation graphite oxide
1) potassium thiosulfate and phosphorus pentoxide are joined in the concentrated sulfuric acid that is stirring, be warmed up to 80 ℃ after waiting to stir, remain on 80 ℃ of stir process 1.5h.Native graphite joins in 80 ℃ the mixed solution, remain on 80 ℃ and stir 4h, be cooled to room temperature, wherein, concentrated sulfuric acid concentration is 98%, the solid-to-liquid ratio of native graphite and the concentrated sulfuric acid is 1: 40, and native graphite and potassium thiosulfate weight ratio are 1: 4, and native graphite and phosphorus pentoxide weight ratio are 1: 4.
2) filter behind the cool to room temperature, place 60 ℃ to dry to constant weight the filter residue after the washing, obtain pre-oxidation graphite.
3) pre-oxidation graphite is joined in the concentrated sulfuric acid of ice-water bath, add potassium permanganate then, remain on 20 ℃ and stir 2h, temperature is risen to 40 ℃ then, keep 30min, persistently overheating to 98 ℃ afterwards, keep 30min, add hydrogen peroxide, add hydrochloric acid then, wherein concentrated sulfuric acid concentration is 98%, and the solid-to-liquid ratio of pre-oxidation graphite and the concentrated sulfuric acid is 1: 30, and pre-oxidation graphite and potassium permanganate weight ratio are 1: 6, hydrogen peroxide concentration is 4%, pre-oxidation graphite and hydrogen peroxide solid-to-liquid ratio are 1: 50, and concentration of hydrochloric acid is 4%, and hydrogen peroxide and hydrochloric acid volume ratio are 1: 10.
4) product is centrifugal, the gained colloid substance is dried to constant weight at 60 ℃, obtain graphite oxide.
2, make the graphene oxide dispersion liquid
Get 0.6g graphite oxide and 300ml distilled water, the graphene oxide dispersion liquid of ultrasonic 1h, wherein graphite oxide and distilled water solid-to-liquid ratio are 1: 500.
3, configuration palladium chloride solution
Get the 0.040g solid palladium chloride and add 10ml watery hydrochloric acid, be stirred to clear solution, wherein the solid-to-liquid ratio of solid palladium chloride and watery hydrochloric acid is that 1: 1000 alkene concentration of hydrochloric acid is 0.5%, the content of palladium is 59% in the solid palladium chloride, and the ratio that contains the weight of palladium in the weight of graphite oxide and the palladium chloride solution is 100: 3.9.
4, prepare graphene-supported palladium catalyst
1) add the 0.5mol/L sodium hydroxide solution, pH transfers to 10 with the graphene oxide dispersion liquid.
2) palladium chloride solution is joined the graphene oxide dispersion liquid, stir 1h.
3) get 20ml distilled water, be placed in the mixture of ice and water and lower the temperature, slowly add the 2g sodium borohydride and be stirred to dissolving fully simultaneously.
4) sodium borohydride solution is joined in the graphite oxide dispersion liquid, stir 6.5h.
5) reaction finishes the back filtration, a large amount of distilled water washing filter residues, and the outflow liquid pH after washing is 7.
6) filter residue is dried to constant weight under 60 ℃, makes the Graphene carried palladium catalyst.
Adopt present embodiment to prepare catalyst and make the electro-catalysis negative electrode, handle 2-chlorophenol solution with electrochemical method, formerly feed hydrogen, under the condition of back aerating oxygen, handle through 120min, 2-chlorophenol clearance reaches 94.8%, the chlorine clearance reaches 91.6%, TOC clearance and reaches 90.9%.
Embodiment 3
1, preparation graphite oxide
1) potassium thiosulfate and phosphorus pentoxide are joined in the concentrated sulfuric acid that is stirring, be warmed up to 80 ℃ after waiting to stir, remain on 80 ℃ of stir process 1h.Native graphite joins in 80 ℃ the mixed solution, remain on 80 ℃ and stir 8h, be cooled to room temperature, wherein, concentrated sulfuric acid concentration is 98%, the solid-to-liquid ratio of native graphite and the concentrated sulfuric acid is 1: 50, and native graphite and potassium thiosulfate weight ratio are 1: 5, and native graphite and phosphorus pentoxide weight ratio are 1: 5.
2) filter behind the cool to room temperature, place 60 ℃ to dry to constant weight the filter residue after the washing, obtain pre-oxidation graphite.
3) pre-oxidation graphite is joined in the concentrated sulfuric acid of ice-water bath, add potassium permanganate then, remain below 20 ℃ and stir 2.5h, temperature is risen to 42 ℃ then, keep 25min, persistently overheating to 92 ℃ afterwards, keep 35min, add hydrogen peroxide, add hydrochloric acid then, wherein concentrated sulfuric acid concentration is 98%, and the solid-to-liquid ratio of pre-oxidation graphite and the concentrated sulfuric acid is 1: 30, and pre-oxidation graphite and potassium permanganate weight ratio are 1: 4, hydrogen peroxide concentration is 2%, pre-oxidation graphite and hydrogen peroxide solid-to-liquid ratio are 1: 200, and concentration of hydrochloric acid is 3.7%, and hydrogen peroxide and hydrochloric acid volume ratio are 1: 7.5.
4) product is centrifugal, the gained colloid substance is dried to constant weight at 60 ℃, obtain graphite oxide.
2, make the graphene oxide dispersion liquid
Get 0.8g graphite oxide and 750ml distilled water, the graphene oxide dispersion liquid of ultrasonic 3h, wherein graphite oxide and distilled water solid-to-liquid ratio are 1: 937.
3, configuration palladium chloride solution
Get the 0.050g solid palladium chloride and add 10ml watery hydrochloric acid, be stirred to clear solution, wherein the solid-to-liquid ratio of solid palladium chloride and watery hydrochloric acid is that 1: 1000 alkene concentration of hydrochloric acid is 0.5%, the content of palladium is 59% in the solid palladium chloride, and the ratio that contains the weight of palladium in the weight of graphite oxide and the palladium chloride solution is 100: 3.7.
4, prepare graphene-supported palladium catalyst
1) add the 0.5mol/L sodium hydroxide solution, pH transfers to 9 with the graphene oxide dispersion liquid.
2) palladium chloride solution is joined the graphene oxide dispersion liquid, stir 1.5h.
3) get 20ml distilled water, be placed in the mixture of ice and water and lower the temperature, slowly add the 1.5g sodium borohydride and be stirred to dissolving fully simultaneously.
4) sodium borohydride solution is joined in the graphite oxide dispersion liquid, stir 8h.
5) reaction finishes the back filtration, a large amount of distilled water washing filter residues, and the outflow liquid pH after washing is 7.
6) filter residue is dried to constant weight under 60 ℃, makes the Graphene carried palladium catalyst.
Adopt the catalyst of present embodiment preparation to make the electro-catalysis negative electrode, handle 2 with electrochemical method, 4-dichloro phenol solution, formerly feed hydrogen, under the condition of back aerating oxygen, handle through 100min, 2,4-two chlorophenol clearances reach 95.1%, and the chlorine clearance reaches 92.2%, TOC clearance and reaches 91.3%.
Claims (7)
1. Catalysts and its preparation method of handling chloride organic wastewater, described catalyst is 0.1-10 by the weight portion proportioning: 100 Metal Palladium and carbonaceous carrier are formed, and carbonaceous carrier selection Graphene is characterized in that comprising following step in sequence:
1) native graphite is carried out pre-oxidation treatment, make pre-oxidation graphite;
2) pre-oxidation graphite is carried out further oxidation processes, make graphite oxide;
3) graphite oxide and distilled water are carried out ultrasonic processing, obtain the graphene oxide dispersion liquid;
4) solid palladium chloride is mixed with watery hydrochloric acid, be configured to solution, add the graphene oxide dispersion liquid then, mix;
5) add alkaline solution, the pH value of regulator solution is 9～10;
6) add sodium borohydride solution, carry out redox reaction;
7) reaction finishes that filter the back, the washing filter residue, and filter residue and drying is to constant weight, namely gets to go back the ortho states palladium and be carried on catalyst on the Graphene.
2. preparation method as claimed in claim 1, it is characterized in that the pre-oxidation treatment described in the step 1) carries out according to following steps: sodium thiosulfate, phosphorus pentoxide are mixed the back under 70～100 ℃ of conditions, add native graphite with the concentrated sulfuric acid, reaction 1～10h, filter and the washing filter residue, dry filter residue then, make the preliminary treatment graphite oxide.
3. preparation method as claimed in claim 1, it is characterized in that step 2) described in further oxidation processes carry out according to following steps: with pre-oxidation graphite, potassium permanganate mix with the concentrated sulfuric acid back under 0～98 ℃ of condition, react 1～10h, add hydrogen peroxide and hydrochloric acid then, centrifugal and gained colloid substance oven dry made graphite oxide.
4. preparation method as claimed in claim 1, the solid-to-liquid ratio that it is characterized in that graphite oxide described in the step 3) and distilled water is 1: 20～200.
5. preparation method as claimed in claim 1 is characterized in that solid palladium chloride described in the step 4) and the ratio of the solid-liquid of hydrochloric acid are 1: 2～200, and the weight portion proportioning of palladium is 100 in graphite oxide and the palladium chloride solution: 0.1-10.
6. preparation method as claimed in claim 1, the mass percent concentration that it is characterized in that alkaline solution described in the step 5) is 1～30%, alkaline solution is selected NaOH or potassium hydroxide solution.
7. preparation method as claimed in claim 1 is characterized in that solid palladium chloride described in the step 6) and sodium borohydride weight portion proportioning are 1: 10～200.
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